S-(2-amidocarboxy-phenyl) esters of phosphorus acids



United States Patent 12 Claims. or. 260943) The present inventionrelates to and has as its objects novel and useful phosphorus containinginsecticidally active compounds.

More specifically this invention is concerned with dia-lkyl-thiolor-thionothiol-phosphoric (-phosphonic, -phosphinic)acid-S-(Z-amidocarboxy-phenyl) esters of the general formula as well asprocesses for their production.

In the above formula R and R denote hydrogen atoms or alkyl radicals, R"and R stand for preferably lower alkyl or alkoxy groups, whilst Yrepresents a hydrogen or halogen atom, a nitro or lower alkyl group, andX is oxygen or sulphur.

0,0-diethyl-thiolor -thionothio-phosphoric acid-S-(Z- carbalkoxy-phenyl)esters, i.e. phosphorylated derivatives of thiosalicylic acid esters,are already known from German patent specifications Nos. 817,057 and885,176.

As stated in the said patent specifications, these compounds are verysuitable for combating sucking and eating insect pests.

In accondance with the present invention is has now been found that thecorresponding dialkylthiolor -thionothiol-phosphoric (-phosphonic,-phosphinic) acid-S- (Z-amido-carboxy-phenyl) esters of the aboveformula i.e. phosphoric (phosphonic, phosphinic) acid derivatives ofoptionally N-substituted thiosalicylic acid amides, which are not yetdescribed in the literature also possess excellent insecticidalpropenties and are therefore eminently suitable as pest control agents.

The production of the compounds according to the invention is carriedout by reacting the corresponding 21amidoor 2-N-alkylarmidoor2-N,N-dia1kylami do-carboxy-phenyl-sulphenic acid halides with0,0-dialkyl- (thiol)phosphorous or alky1-(thiol)phosphonous acid-O-alkyl esters or dialkyl- (thiol)phosphinous acids.

However, it is also possible to use Z-halo-carboxyphenyl-sulphenic acidhalides as starting materials and to react these first with the said(thiol)phosphorous (-phosphonous) acid esters or (thiol)phosphinousacids and subsequently, expediently without isolating the intermediateproducts, with ammonia, N-alkylor N,N-dialkylamines.

The course of the reaction according to the present 3,277,214 PatentedOct. 4, 1966 process may be illustrated in more detail ing reactionscheme:

by the follow- In the preceding equations, the symbols R to R', X and Yhave the same significance as given above, Whilst Hal stands for ahalogen atom.

The reaction according to the invention is preferably 25 carried out inthe presence of inert organic solvents. Chlorinated aliphatichydrocarbons such as methylene chloride, chloroform or carbontetrachloride have proved to be especially suitable.

The Z-haloor optionally N-substituted 2-amido carboxy-phenyl-sulphenicacid halides required as starting materials for the inventive processare produced by splitting the corresponding bis-(Z-haloor 2-amido-, 2-N-alkylamidoor 2-N,N-dialkylamido-carboxy-pheny1)-disulphides withhalogenating agents such as elementary chlorine or bromine or withsulphuryl chloride. It is not necessary to isolate the sulphenic acidhalides in substance; the reaction products of the above-mentionedbis-(Z-haloor Z-amido-carboxy-phenyl)-disulphides and the halogenatingagents can directly be reacted according to the present invention withthe dialkyl(thiol)-phosphorous (-phophonous, -phosph-inous) acidderivatives or, Without isolation of the intermediate products,subsequently reacted with ammonia, N-alkylor N,N-dialkylamines, ifdesired.

The compounds obtainable according to the process of the invention arein part obtained in crystalline form, but some are colourless toslightly coloured oils which cannot be distilled without decompositioneven in a vacuum.

As already mentioned above, the products of the present invention aredistinguished by an outstanding action against a number of insect pests.

The new compounds very efiectively kill insects like aphids, spidermites, ticks, blowfly larvae, caterpillars, flies etc. They distinguishthemselves especially by -a good contact-insecticidal activity in partalso by an ovicidal effect and mostly also by an outstanding systemicaction. At the same time they have an activity on eating insects such ascaterpillars. Most surprisingly they are of remarkably low toxicityagainst warm-blooded creatures. They may be used in the same manner asother known phosphoric insecticides, i.e. in a concentration from about0.00001% to about 1%, diluted or extended with suitable solid or liquidcarriers or diluents. Ex-

amples of such solid carriers are talc, chalk, bentonite, clay and thelike, as liquid carriers there may be mentioned water (if necessary withcommercial emulsifiers), alcohols, especially lower alcohols such asmethanol or ethanol, ketones, especially lower ketones such as acetoneor methyl ethyl ketone, liquid hydrocarbons and the like. The newcompounds may furthermore be used in combination with each other or withknown insecticides, fertilizers etc.

As examples for the special utility the inventive compounds of thefollowing formulae have been tested against aphids and spider mites.Aqueous dilutions of these compounds have been prepared by mixing theactive ingredients with the same amounts of dimethyl formamide as anauxiliary solvent adding thereto 20% by weight referred to activeingredient of a commercial emulsifier consisting of a benzyl hydroxypolyglycol ether containing about to glycol ethers, and diluting thispremixture at last with water to the desired concentration indicated inthe following paragraphs. The tests have been carried out as follows:

(a) Against aphids (species Doralis fabae): heavily infested bean plants(Vicia faba) have been sprayed drip wet with solutions as preparedabove. The effect has been determined after 24 hours by counting thedead pests either on the surface of the soil or still remaining on theplants. The following results have been obtained:

Aqueous concentration (in Killing rate Compound percent activeingrcdicnt/ (in percent) water) III 0 .01 100 (b) Against spider mites:Bean plants (Phaseolus vulgaris) of about 15 inches height are sprayeddrip wet with solutions as prepared above and in a concentration asshown below. The bean plants have been infested heavily with thetwo-spotted spider (species T etranychus telarius). Evaluation has beencarried out after 24 hours, 48 hours and 8 days. The following resultshave been 1 Ovicidal action.

Regarding the insecticidal properties the inventive products are clearlysuperior to the compounds of analogous Insecticidal activityAdministration Aqueous Compound against concentration Killing (inpercent rate (in active inpercent) gredient/ water) 0 0 02115 Aphids(contact 0. 01 50 actio SP Spider mites H 0.01 O \O C111 Aphids(systemic 0. 1 0

action).

C O O C H (Known from German Patent No. 817,057).

0 0 0 11 Aphids (contact 0.01 100 actio 0. 001 60 S -P Spider mites 0.001 100 \O OzH Aphids (systemic 0. 1 100 action).

C O NH 0 Ha (According to the invention S OC2H5 Aphids (contact 0.05 100action). S P Spider mites \0 Calls Aphids (systemic action).

C O 0 CH (Known from German Patent No. 885,176.)

S O OzHt Aphids (contact 0.01 100 action). 0. 001 60 S P Spider mites H0. 001 100 0. 001 0 0211 Aphids (systemic 0. 1

action).

C O N H C H (According to the invention).

On account of their excellent insecticidal properties the compoundsobtainable according to the invention are used as pest control agents,chiefly for plant protection and in the veterinary field.

The following examples are given for the purpose of illustrating theinvention as claimed.

Example 1 CONHCH 100 g. (0.3 mol) ofbis-(Z-N-methylamidocarboxyphenyl)-disulphide (prepared according to A.Reissert and E. Mann's in Berichte der deutschen chemischenGesellschaft, vol. 61 (1928), page 1312; MP. 216.5 C.) are suspended in700 cc. of chloroform. To this suspension 45 g. (0.33 mol) of sulphurylchloride are added dropwise at 20 to 25 C. with stirring and ex ternalcooling, the mixture is subsequently stirred at room temperature for afurther 10 minutes and then treated dropwise with 92 g. (0.66 mol) of0,0-diethylphosphorous acid ester. A strong exothermic reactio occurs.An internal temperature of 20 to 30 C. is maintained by cooling thereaction mixture with icewater. After stirring the mixture for one hour,the sola vent is distilled oil and the distillation residue stirred withwater. The separated oil is taken up in benzene and the benzene solutionbriefly Washed with a sodium bicarbonate solution. The organic phase isfinally dried over sodium sulphate, the solvent distilled off, and asesidue there are obtained 122 g. (57% of the theoretical yield) of the0,0-diethyl-thiolphosphoric acid-S-(Z-N- methylamidocarboxy-phenyl)ester in the form of a thickly liquid, yellow-orange coloured oil whichcannot be distilled .even in a high vacuum.

Analysis.Calculated for C H O NSP (mol. weight 303.3): N, 4.62%; 5,10.57%; P, 10.21%. Found: N, 4.60%; S, 10.64%; P, 10.09%.

Aphids are completely destroyed by 0.01% solutions and spider mites evenby 0.001% solutions of the compound. Moreover the product shows anovicidal activity against the eggs of spider mites.

Example 2 37 g. (0.275 mol) of sulphuryl chloride are added dropwisewith stirring and external cooling to a suspension of 83 g. (0.25 mol)of bis-(2-N-rnethylamidocarboxy-phenyl)-disulphide in 700 cc. ofchloroform, the mixture is further stirred for minutes, treated dropwisewith 69 g. (0.55 mol) of 0,0-dimethyl-thiolphosphorous acid ester, andsubsequently stirred for a further 2 /2 hours at 20 to 25 C., until thesolid components are dissolved. The reaction mixture is then stirredwith Water, the organic phase separated and washed with a potassiumcarbonate solution until the reaction is neutral. After distilling offthe solvent, the 0,0-dimethyl-thionothiolphosphoricacid-S-(2-N-methylamidocarboxy-phenyl) ester remains in the form of anoil which solidifies in a crystalline form upon trituration withpetroleum ether. After recrystallisation from a mixture of equal partsof acetic acid ethyl ester and petroleum ether, the compound is obtainedas almost colourless small needles of MP. 112 to 113 C. The yieldamounts to 105 g. (56.7% of the theoretical).

Analysis.Calculated for C H O NS P (mol. weight 291.3): N, 4.81%; P,10.64%. Found: N, 4.94%; P, 10.98%.

Aphids and spider mites are killed 100% by 0.01% solutions of the ester.The compound also exhibits an ovicidal activity against the eggs ofspider mites.

Example 3 83 g. (0.25 mol) ofbis-(Z-N-methylamidocarboxyphenyl)-disulphide are suspended in 700 cc.of chloroform, 37 g. (0.275 mol) of sulphuryl chloride (22.3 cc.) areadded dropwise with stirring to this suspension at 20 to 25 C., whilecooling, the mixture is stirred for a further 10 minutes andsubsequently mixed dropwise with 85 g. (0.55 mol) of0,0-diethyl-thiolphosphorous acid ester. The temperature of the reactionmixture rises to 34 to 35 C. in the course of 2 hours whereby all solidconstituents are dissolved. After distilling off the solvent, theresidue solidifies in crystalline form. The0,0-diethylthiono-thiolphosphoric acid-S-(2-N-methyl-amidocarboxyphenyl)ester can be recrystallised from an ether/petroleum ether mixture andthen melts at 76 to 78 C. The yield amounts to 122 g. (76.4% of thetheoretical).

Analysis.-Calculated for C H O NS P (mol. weight 319.4): N, 4.39%; S,20.08%; P, 9.70%. Found: N, 4.42%; S, 20.41%; P, 9.72%.

On rats per es the mean toxicity of the compound (DL amounts to 5 mg.per kg. of animal.

Aphids and spider mites are completely destroyed by 0.01 solutions ofthe compound, which moreover shows an ovicidal activity against the eggsof spider mites.

Example 4 A solution of 36 g. (0.1 mol) ofbis-(2-N,N-dimethylamidocarboxy-phenyl)-disulphidc (M.P. 132 C.) in 150cc. of methylene chloride is treated dropwise at 20 C. with 15 g. (0.11mol) of sulphuryl chloride. A weak exothermic reaction occurs. Thetemperature of the mixture is maintained at 20 to 25 C. by appropriateexternal cooling. 10 minutes after the reaction is completed, 27.5

g. (0.25 mol) of 0,0-dimethyl-phosphorous acid ester are added dropwiseto the reaction mixture, the solvent is distilled off after a further10. minutes, the residue is stirred with water and the separated oiltaken up in methylene chloride. The methylene chloride solution iswashed with water until the reaction is neutral, the organic phase isthen dried over sodium sulphate and the solvent again distilled off. Theresidue solidifies in crystalline form. After recrystallisation fromacetic acid ethyl ester, the 0,0-dimethyl-thiolphosphoric acid-S-(2-N,N-dimethylamidocarboxy-phenyl) ester is obtained in the form ofcoarse, colourless crystals of MP. 76 C. The yield amounts to 45 g. (78%of the theoretical).

Analysis.-Calculated for C H O NSP (mol. weight 289.3): N, 4.84%; S,11.08%; P, 10.71%. Found: N, 4.64%; S, 11.42%; P, 10.57%.

On rats per os the acute toxicity of the compound (DL amounts to 25 mg.per kg. of animal.

Spider mites are destroyed by 0.001% solutions, aphids by 0.01%solutions of the ester. The compound also shows an ovicidal actionagainst the eggs of spider mites.

Example 5 36 g. (0.1 mol) ofbis-(2-N,N-dimethylamidocarboxyphenyl)-disulphide are dissolved in cc.of methylene chloride. 15 g. (0.11 mol) of sulphuryl chloride are addeddropwise to this solution at 20 C. whereby 'a weak exothermic reactionoccurs. The temperature of the mixture is maintained at 20 to 25 C. byappropriate external cooling. 10 minutes after the reaction iscompleted, the reaction mixture is treated with 35 g. (0.25 mol) of0,0-diethyl-phosphorous acid ester, the solvent distilled off after afurther 10 minutes, the residue stirred with water and the separated oiltaken up in methylene chloride. The methylene chloride solution iswashed with water until it reacts neutrally, dried over sodium sulphate,and the solvent is finally again distilled off. 54 g. (87.5% of thetheoretical yield) of 0,0-diethylthiolphosphoric acid S (2 N,Ndimethylamido carboxy-phenyl) ester are obtained as a thickly liquid,yellow-green oil which is not distillable.

Analysis.-Calculated for C H O NSP (m-ol weight 317.3): N, 4.42%; S,10.10%; P, 9.76%. Found: N, 4.41%; S, 10.06%; P, 9.84%.

On rats per es the acute toxicity of the compound (DL )amounts to 2.5mg. per kg. of animal.

Aphids and spider mites are completely destroyed by 0.001% solutions ofthe compound. The product also possesses an ovicidal action against theeggs of spider mites.

Example 6 15 g. (0.11 mol) of sulphuryl chloride are added dropwise at20 C. to'a solution of 36 g. (0.1 mol) of bis- (2 N,Ndimethylamidocarboxy phenyl) disulphide in 150 cc. of methylenechloride. A weak exothermic reaction occurs. The temperature of themixture is maintained at 20 to 25 C. by appropriate external cooling.minutes after the addition is completed 28 g. (0.22 mol) of0,0-dimethyl-thiolphosphorous acid ester are added dropwise withstirring to the reaction mixture, the latter is stirred for a further 10minutes and then washed with water and a sodium bicarbonate solutionuntil it reacts neutrally. After drying the organic phase over sodiumsulphate, the solvent is distilled off. The distillation residuesolidifies in crystalline form. It is recrystallised from ether(solubility about 1 g./2 cc.), whereupon the0,0-dimethyl-thionothiol-S-(2-N,N-dimethylamidocarboxy-phenyl) ester isobtained in the form of coarse, colourless crystals of M.P. 67 C. Theyield amounts to 50 g. (83.7% of the theoretical).

Analysis.Calculated for C H O NS P (mol weight 305.4); N, 4.58%; S,20.99%; P, 10.14%. Found: N, 44.44%; S, 20.53%; P, 10.12%.

Aphids and spider mites are killed 100% by 0.01% solutions of the ester,which also shows an ovicidal action against the eggs of spider mites.

Example 7 36 g. (0.1 mol) ofbis-(2-N,N-dimethylamidocarboxyphenyl)-disulphide are dissolved in 150cc. of methylene chloride, and g. (0.11 mol) of sulphuryl chloride areadded dropwise to this solution at C. A weak exothermic reaction occurs.The temperature of the mixture is maintained at 20 to C. by externalcooling. 10 minutes after the addition is completed, the reactionmixture is treated dropwise while stirring with 33 g. (0.22 mol) of0,0-diethyl-thiolphosphorous acid ester, then stirred for a further 10minutes and finally washed with water and a sodium bicarbonate solution,until the reaction is neutral. After drying the organic Phase oversodium sulphate, the solvent is distilled off, and the 0,0- diethylthionothiolphosphoric acid S (2 N,N dimethylamidocarboxy-phenyl) esteris obtained in the form of a thickly liquid greenish yellow oil which isnot distillable. The yield amounts to 57 g. (86.4% of the theoretical)Analysis.Calculated for C 'H O NS P (mol weight 333.4): N, 4.20%; S,19.23%; P, 9.29%. Found: N, 3.62%; S, 20.06%; P, 9.32%.

On rats per os the acute toxicity of the compound (-DL amounts to 10 mg.per kg. of animal.

Aphids and spider mites are complete-1y kill by 0.01% solutions of thecompound. The ester also possesses an ovicidal activity against the eggsof spider mites.

Example 8 68.5 g. (0.2 mol) of bis-(2-chlorocarboxy-phenyl)-disulphideare suspended in 250 cc. of methylene chloride. g. (0.22 mol) ofsulphuryl chloride are added dropwise with stirring to this suspensionat 20 C., the reaction mixture is stirred at room temperature for 10minutes and subsequently treated dropwise at 10 to 20 C., with externalcooling, with 55 g. (0.5 mol) of O,O-dimethy1- phosphorous acid ester.After stirring for a short time, this mixture is added dropwise to 154cc. of a 27.2% methylam-ine solution (1.25 mol), the reaction mixture isfurther stirred for hour, the organic phase separated and the solventdistilled off. The remaining oil is taken up in benzene, the benzenesolution washed with a potassium carbonate solution, the organic layerdried and freed from the solvent. The residual oil solidifies incrystalline form. By recrystallisation from a benezene/petroleum ethermixture, the 0,0-dimethyl-thiolphosphoric acid-S-(2-N-methylamidocarboxy-phenyl) ester is obtained in the form ofcolourless small needles of M.P. C. The yield amounts to 35 g. (31.9% ofthe theoretical).

Analysis.-C-alculated for C H O NSP (mol. weight 275.3): N, 5.08%; S,11.65%; P, 11.25%. Found: N, 4.96%; S, 11.98%; P, 1 1.49%.

Aphids and spider mites are killed by 0.001 solutions of the ester,which moreover possesses an ovicidal activity against the eggs of spidermites.

Example 9 OONH:

30 g. (0.22 mol) of sulphuryl chloride are added dropwise with stirringat 20 C. to a suspension of 68.5 g. (0.2 mol) ofbis-(2-chloroca-rboxy-phenyl)disulphide in 250 cc. of methylenechloride, and then the mixture is stirred at room temperature for 15minutes. The reaction mixture is subsequently treated at 20 to 25 C.,with external cooling, with 70 g. (0.5 mol) of 0,0-diethyl-phosphorousacid ester and then added dropwise at 20 to 30 C., with further cooling,to a solution of cc. of concentrated ammonia in 110 cc. of water. Themixture is then further stirred for 1 hour, the methylene chloride layerseparated and washed once with water. After drying the organic phaseover sodium sulphate, the solvent is distilled oil. The residuesolidifies in crystalline form. By recrystallising it from abenzene/ether mixture, 100 g. (86. 6% of the theoretical yield) of0,0-diethyl-thiolphosphor-ic acid- S-(2-amidocarboxy-phenyl) ester areobtained in the form of colourless crystals of M.P. 92 C.

Analysis.-Calculated for C H O NSP (mol. weight 289.3): N, 4.84%; S,11.08%; P, 10.71%. Found: N, 4.89%; S, 10.98%; P, 11.05%.

Aphids and spider mites are completely destroyed by 0.01% solutions ofthe compound.

Example 10 ll SP (0 CH CONHz 68.5 g. (0.2 mol) ofbis-(2-chlorocarboxy-phenyl)-disulphide are suspended with stirring in250 cc. of methylene chloride, 30 g. (0.22 mol) of sulphuryl chlorideare added dropwise to this suspension at 20 C., and stirring iscontinued at room temperature for 15 minutes. The reaction mixture isthen treated at 20 to 25 C., with ex ternal cooling, with 63 g. (0.5mol) of 0,0-dimethyl-thiolphosphorous acid ester. This mixture is thenadded dropwise, with further cooling and stirring, to a solution of 110cc. of concentrated ammonia in 110 cc. of water, the reaction mixture isfurther stirred for 1 hour, the methylene chloride layer separated andwashed once with water. After drying the organic phase over sodiumsulphate, the solvent is distilled oil. The residue solidifies in acrystalline form. By recrystallisation from benzene 93 g. (84.6% of thetheoretical yield) of 0,0-dimethyl- 9 thionothiolphosphoric acid -S-(2-amidocarboxy-phenyl) ester are obtained in the form of colourlesscrystals of MJP. 76 C.

Spider mites are completely destroyed by 0.1% solutions, aphids even by0.01% solutions of the ester.

Example 11 C ONHa 68.5 g. (0.2 mol) ofbis-2-chlorocarboxy-phenyl)-disulphide are suspended in 250 cc. ofmethylene chloride. 30 g. (0.22 mol) of sulphuryl chloride are addeddropwise with stirring to this suspension at 20 C., the reaction mixtureis stirred for a further 15 minutes at room temperature and finallytreated at 20 to 25 C., with external cooling, with 70 g. (0.5 mol) of0,0-diethyl-thiolphosphorous acid ester. This mixture is then addeddropwise at 20 to 30 C., with further cooling and stirring to 110 cc. ofconcentrated ammonia dissolved in 110 cc. of water, the whole is furtherstirred for 1 hour, the organic phase separated and washed once withwater. After drying the methylene chloride solution over sodiumsulphate, the solvent is distilled off. The remaining residue solidifiesin crystalline form. By recrystallisation from a benzene/ petroleumether mixture the 0,0-diethylthionothiolphosphoric acidS-(2-amidocarboxy-phenyl) ester is obtained as a colourless crystallinepowder of MP. 50 C. The yield amounts to 107 g. (87.5% of thetheoretical).

Analysis.-Calculated for C H O NS P (mol. weight 305.4): N, 4.59%; S,21.00%; P, 10.14%. Found: N, 4.56%; S, 20.07%; P, 9.85%.

Spider mites are completely destroyed by 0.01% solutions, of thecompound, which also shows an ovicidal activity against the eggs of thesaid pests.

Example 12 CONHCH To a suspension of 29 g. (0.0875 mol) of bis-(2-N-methyl-amidocarboXy-phenyl)-disulphide in 100 cc. of chloroform 13 g.(0.096 mol) of sulphuryl chloride are first added dropwise at 20 to 25C., with stirring and external cooling, and subsequently, after stirringfor a short time, 23.4 g. (0.192 mol) of ethyl-thiolphosphonous acid-O-ethyl ester are added at the specified temperature with furthercooling. The reaction mixture is further stirred for a short time, thesolvent is then distilled off, the residue taken up in benzene andworked up in the manner repeatedly described above. 33 g, (72.2% of thetheoretical yield) of the ethyl-thiolphosphonic acid-O-ethyl-S-(2-N-methylamidocarboxyphenyl) ester are obtained in the form of a greenishyellow oil which is not distillable without decomposition, even understrongly reduced pressure.

Mosquito larvae are completely destroyed by 0.001% solutions and grainweevils by 0.1% solutions of the compound.

I claim: 1. A compound of the formula ill /Ri SP wherein R and R standfor members selected from the group consisting of lower alkyl having upto 4 carbon atoms and lower alkoxy having up to 4 carbon atoms, R

and R stand for members selected from the group consisting of hydrogenand lower alkyl having up to 4 carbon atoms and X is a chalkogen havingan atomic weight less than 40.

2. The compound according to claim 1 wherein R and R stand for alkoxy, Rstands for hydrogen and R stands for alkyl.

3. The compound according to claim 1 wherein R and R stand for alkoxyand R and R stand for alkyl.

4. The compound according to claim 1 wherein R and R stand for alkoXyand R and R stand for hydrogen.

5. The compound according to claim 1 wherein R stands for alkyl, Rstands for alkoxy, R stands for hydrogen and R stands for alkyl.

6. The compound of the formula ll S 2 B):

CONHCH 7. The compound of the formula s l S- (0 02301 o ONHOH,

8. The compound of the formula CON(CH3);

9. The compound of the formula i 8-? (0 CH 3 o o N(CH,) 2

10. The compound of the formula i S H3):

CONHCH;

11. The compound of the formula 12. The compound of the formulaReferences Cited by the Examiner UNITED STATES PATENTS 2,915,547 12/1959Atherton 260461 2,944,074 7/1960 Atherton 260-461 3,099,597 7/ 1963Chupp et a1 260-461 X FOREIGN PATENTS 1,129,484 5/ 1962 Germany.

OTHER REFERENCES Schrader: 615,669, Sept. 28, 1962, Belgium (28 pagesspec.; no dwg.) Abstracted in Chem. Abst., vol. 58, C01. 11402, May 27,1963.

CHARLES B. PARKER, Primary Examiner. FRANK M. SIKORA, AssistantExaminer.

1. A COMPOUND OF THE FORMULA